##############################################################################
#                                                                            #
# This CIF contains the data in a paper accepted for publication in          #
# Acta Crystallographica Section E. It conforms to the requirements of       #
# Notes for Authors for Acta Crystallographica Section E, and has been       #
# peer reviewed under the auspices of the IUCr Commission on Journals.       #
#                                                                            #
# Full details of the Crystallographic Information File format               #
# are given in the paper "The Crystallographic Information File (CIF):       #
# a New Standard Archive File for Crystallography" by S. R. Hall, F. H.      #
# Allen and I. D. Brown [Acta Cryst. (1991), A47, 655-685].                  #
#                                                                            #
# The current version of the core CIF dictionary is obtainable from          #
# ftp://ftp.iucr.org/pub/cif_core.dic.                                       #
#                                                                            #
# Software is freely available for graphical display of the structure(s)     #
# in this CIF. For information consult the CIF software page                 #
# http://www.iucr.org/resources/cif/software.                                #
#                                                                            #
# This file may be used for bona fide research purposes within the           #
# scientific community so long as proper attribution is given to the journal # 
# article from which it was obtained.                                        #
#                                                                            #
##############################################################################
data_I
_database_code_depnum_ccdc_archive 'CCDC 1489622'
_audit_creation_method     SHELXL-2014/6
_journal_date_recd_electronic     2016-06-09
_journal_date_accepted     2016-07-01
_journal_name_full     'Acta Crystallographica, Section E'
_journal_year     2016
_journal_volume     72
_journal_issue      8
_journal_page_first     1064
_journal_page_last     1067
_journal_paper_category     GM
_journal_paper_doi     10.1107/S2056989016010719
_journal_coeditor_code     GK2663
_publ_contact_author_name     'Gellert Mezei'
_publ_contact_author_address
;
Department of Chemistry, Western Michigan University, Kalamazoo, Michigan, USA
;
_publ_contact_author_email     gellert.mezei@wmich.edu
_publ_contact_author_fax     ?
_publ_contact_author_phone     ?
_publ_section_title
;
Sulfate-bridged dimeric trinuclear copper(II)--pyrazolate complex with three
different terminal ligands
;
_publ_section_title_footnote     .
loop_
    _publ_author_name
    _publ_author_footnote
    _publ_author_address
    'Mezei, Gellert' .
;
Department of Chemistry, Western Michigan University, Kalamazoo, Michigan, USA
;
_publ_section_synopsis
;\
The crystal structure of the first trinuclear copper--pyrazolate (pz) complex
with three different terminal ligands, including a strongly binding sulfate,
is reported. The sulfate ion also acts as bridging ligand, leading to a
dimeric structure,
[Cu₃(μ₃-OH)(μ-4-Cl-pz)₃(μ₄-SO₄)(DMF)(H₂O)]\
₂\\cdot4DMF\\cdot2H₂O.
;
_chemical_name_systematic
;\
Diaquahexakis(μ-4-chloropyrazolato-κ²N:N')\
bis(N,N-dimethylformamide)di-μ₃-hydroxido-\
bis(μ₄-sulfato-κ⁴O:O':O'':O'')hexacopper(II)
N,N-dimethylformamide tetrasolvate dihydrate
;
_chemical_name_common     ?
_chemical_formula_moiety     'C24 H32 Cl6 Cu6 N14 O14 S2, 4(C3 H7 N O), 2(H2 O)'
_chemical_formula_sum     'C36 H64 Cl6 Cu6 N18 O20 S2'
_chemical_formula_iupac
   '[Cu6 (O H)2 (S O4)2 (C3 H2 Cl N2)6 (C3 H7 N O)2 (H2 O)2], 4C3 H7 N O, 2H2 O'
_chemical_formula_weight     1727.11
_chemical_melting_point     ?
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system     monoclinic
_space_group_name_H-M_alt     'P 21/n'
_space_group_name_Hall     '-P 2yn'
loop_
    _space_group_symop_operation_xyz
    'x, y, z'
    '-x+1/2, y+1/2, -z+1/2'
    '-x, -y, -z'
    'x-1/2, -y-1/2, z-1/2'
_cell_length_a     12.70380(10)
_cell_length_b     16.5265(2)
_cell_length_c     16.6830(2)
_cell_angle_alpha     90
_cell_angle_beta     109.7740(10)
_cell_angle_gamma     90
_cell_volume     3296.05(6)
_cell_formula_units_Z     2
_cell_measurement_reflns_used     6640
_cell_measurement_theta_min     2.59
_cell_measurement_theta_max     26.94
_cell_measurement_temperature     100(2)
_exptl_crystal_description     'prism'
_exptl_crystal_colour     'blue'
_exptl_crystal_size_max     0.240
_exptl_crystal_size_mid     0.100
_exptl_crystal_size_min     0.050
_exptl_crystal_density_diffrn     1.740
_exptl_crystal_density_meas     ?
_exptl_crystal_density_method     ?
_exptl_crystal_F_000     1748
_exptl_absorpt_coefficient_mu     2.286
_exptl_absorpt_correction_type     multi-scan
_exptl_absorpt_process_details
;
(SADABS; Bruker, 2014)
;
_shelx_estimated_absorpt_T_min     0.610
_shelx_estimated_absorpt_T_max     0.894
_exptl_absorpt_correction_T_min     0.6100
_exptl_absorpt_correction_T_max     0.8943
_diffrn_ambient_temperature     100(2)
_diffrn_radiation_type     MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_measurement_device_type     'Bruker APEXII CCD'
_diffrn_measurement_method     'φ and ω scans'
_diffrn_detector_area_resol_mean     ?
_diffrn_reflns_number     39853
_diffrn_reflns_av_R_equivalents     0.0607
_diffrn_reflns_theta_min     1.758
_diffrn_reflns_theta_max     28.718
_diffrn_reflns_theta_full     25.242
_diffrn_measured_fraction_theta_max     0.997
_diffrn_measured_fraction_theta_full     1.000
_diffrn_reflns_limit_h_min     -17
_diffrn_reflns_limit_h_max     17
_diffrn_reflns_limit_k_min     -20
_diffrn_reflns_limit_k_max     22
_diffrn_reflns_limit_l_min     -22
_diffrn_reflns_limit_l_max     22
_refine_special_details     ?
_reflns_number_total     8504
_reflns_number_gt     6351
_reflns_threshold_expression     'I > 2σ(I)'
_refine_ls_structure_factor_coef     Fsqd
_refine_ls_matrix_type     full
_refine_ls_R_factor_all     0.0595
_refine_ls_R_factor_gt     0.0351
_refine_ls_wR_factor_gt     0.0672
_refine_ls_wR_factor_ref     0.0751
_refine_ls_goodness_of_fit_ref     1.014
_refine_ls_restrained_S_all     1.014
_refine_ls_number_reflns     8504
_refine_ls_number_parameters     418
_refine_ls_number_restraints     5
_refine_ls_hydrogen_treatment     mixed
_refine_ls_weighting_scheme     calc
_refine_ls_weighting_details
              'w=1/[σ²(Fo²)+(0.0294P)²+1.2380P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_hydrogens     mixed
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary     ?
_refine_ls_shift/su_max     0.001
_refine_ls_shift/su_mean     0.000
_refine_diff_density_max     0.592
_refine_diff_density_min     -0.515
_refine_ls_extinction_method     none
_refine_ls_extinction_coef     .
loop_
    _atom_type_symbol
    _atom_type_description
    _atom_type_scat_dispersion_real
    _atom_type_scat_dispersion_imag
    _atom_type_scat_source
    'C' 'C' 0.0033 0.0016
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
    'H' 'H' 0.0000 0.0000
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
    'N' 'N' 0.0061 0.0033
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
    'O' 'O' 0.0106 0.0060
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
    'S' 'S' 0.1246 0.1234
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
    'Cu' 'Cu' 0.3201 1.2651
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
    'Cl' 'Cl' 0.1484 0.1585
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_computing_data_collection
;
APEX2 (Bruker, 2014)
;
_computing_cell_refinement
;
SAINT (Bruker, 2014)
;
_computing_data_reduction
;
SAINT (Bruker, 2014)
;
_computing_structure_solution
;
SHELXS97 (Sheldrick, 2008)
;
_computing_structure_refinement
;
SHELXL2014 (Sheldrick, 2015)
;
_computing_molecular_graphics
;
SHELXTL (Sheldrick, 2008)
;
_computing_publication_material
;
SHELXTL (Sheldrick, 2008)
;
loop_
    _atom_site_type_symbol
    _atom_site_label
    _atom_site_fract_x
    _atom_site_fract_y
    _atom_site_fract_z
    _atom_site_U_iso_or_equiv
    _atom_site_adp_type
    _atom_site_calc_flag
    _atom_site_occupancy
    _atom_site_disorder_assembly
    _atom_site_disorder_group
    Cu Cu1 0.88533(2) 0.98432(2) 0.92266(2) 0.01205(7) Uani d 1 . .
    Cu Cu2 0.84732(2) 0.78607(2) 0.89552(2) 0.01339(8) Uani d 1 . .
    Cu Cu3 0.71256(3) 0.89070(2) 1.00006(2) 0.01415(8) Uani d 1 . .
    S S1 1.02182(5) 1.14500(4) 0.90916(4) 0.01287(13) Uani d 1 . .
    Cl Cl1 1.14671(7) 0.88248(5) 0.71858(6) 0.0362(2) Uani d 1 . .
    Cl Cl2 0.50045(6) 0.57973(5) 0.93424(6) 0.0375(2) Uani d 1 . .
    Cl Cl3 0.69134(6) 1.23152(4) 1.07089(5) 0.02872(17) Uani d 1 . .
    O O1 0.78020(14) 0.89300(10) 0.90866(11) 0.0124(4) Uani d 1 . .
    H H1O 0.7316(19) 0.8995(17) 0.8661(13) 0.015 Uiso d 1 . .
    O O2 1.00215(13) 1.06890(10) 0.95164(11) 0.0137(4) Uani d 1 . .
    O O3 0.92608(14) 1.15827(11) 0.83199(12) 0.0181(4) Uani d 1 . .
    O O4 1.12603(14) 1.13455(11) 0.89049(12) 0.0162(4) Uani d 1 . .
    O O5 1.03357(14) 1.21179(10) 0.96983(11) 0.0156(4) Uani d 1 . .
    O O6 0.62509(15) 0.88937(11) 1.07932(12) 0.0193(4) Uani d 1 . .
    O O7 0.89793(15) 0.68175(11) 0.86138(13) 0.0191(4) Uani d 1 . .
    H H7A 0.855(2) 0.6528(16) 0.8274(16) 0.023 Uiso d 1 . .
    H H7B 0.9493(19) 0.6535(16) 0.8930(17) 0.023 Uiso d 1 . .
    O O8 0.07007(16) 0.59491(12) -0.04174(13) 0.0265(5) Uani d 1 . .
    O O9 -0.13195(15) 0.43846(12) 0.74393(13) 0.0264(5) Uani d 1 . .
    O O10 0.24177(18) 0.42323(14) 0.23718(17) 0.0412(7) Uani d 1 . .
    H H10A 0.293(2) 0.401(2) 0.2728(19) 0.049 Uiso d 1 . .
    H H10B 0.219(3) 0.4655(15) 0.251(2) 0.049 Uiso d 1 . .
    N N1 0.95307(17) 0.92644(13) 0.85102(14) 0.0147(5) Uani d 1 . .
    N N2 0.94773(17) 0.84403(13) 0.84797(14) 0.0149(5) Uani d 1 . .
    N N3 0.72096(17) 0.73695(13) 0.92013(14) 0.0155(5) Uani d 1 . .
    N N4 0.67343(17) 0.77874(13) 0.96960(14) 0.0154(5) Uani d 1 . .
    N N5 0.72004(17) 1.00879(13) 1.00420(14) 0.0156(5) Uani d 1 . .
    N N6 0.79401(16) 1.04688(13) 0.97334(14) 0.0142(5) Uani d 1 . .
    N N7 0.61860(18) 0.90095(14) 1.21195(15) 0.0201(5) Uani d 1 . .
    N N8 0.21667(19) 0.62870(14) 0.07710(15) 0.0218(5) Uani d 1 . .
    N N9 0.03464(18) 0.37758(13) 0.81585(15) 0.0195(5) Uani d 1 . .
    C C1 1.0125(2) 0.81766(16) 0.80436(17) 0.0175(6) Uani d 1 . .
    H H1 1.0244 0.7638 0.7937 0.021 Uiso calc 1 . .
    C C2 1.0585(2) 0.88365(17) 0.77797(18) 0.0196(6) Uani d 1 . .
    C C3 1.0202(2) 0.95107(17) 0.80841(17) 0.0183(6) Uani d 1 . .
    H H3 1.0378 1.0045 0.8008 0.022 Uiso calc 1 . .
    C C4 0.5943(2) 0.73193(16) 0.98217(18) 0.0185(6) Uani d 1 . .
    H H4A 0.5498 0.7459 1.0143 0.022 Uiso calc 1 . .
    C C5 0.5894(2) 0.65981(16) 0.93968(19) 0.0207(6) Uani d 1 . .
    C C6 0.6705(2) 0.66438(16) 0.90177(19) 0.0201(6) Uani d 1 . .
    H H6 0.6874 0.6241 0.8691 0.024 Uiso calc 1 . .
    C C7 0.7943(2) 1.12579(16) 0.99150(18) 0.0175(6) Uani d 1 . .
    H H7 0.8377 1.1651 0.9777 0.021 Uiso calc 1 . .
    C C8 0.7200(2) 1.13943(16) 1.03396(18) 0.0192(6) Uani d 1 . .
    C C9 0.6751(2) 1.06498(16) 1.04087(18) 0.0187(6) Uani d 1 . .
    H H9 0.6221 1.0552 1.0668 0.022 Uiso calc 1 . .
    C C10 0.6727(2) 0.89642(16) 1.15752(19) 0.0199(6) Uani d 1 . .
    H H10 0.7504 0.8986 1.1785 0.024 Uiso calc 1 . .
    C C11 0.4967(2) 0.8972(2) 1.1816(2) 0.0321(8) Uani d 1 . .
    H H11A 0.4714 0.8602 1.1347 0.048 Uiso calc 1 . .
    H H11B 0.4667 0.9500 1.1634 0.048 Uiso calc 1 . .
    H H11C 0.4719 0.8790 1.2269 0.048 Uiso calc 1 . .
    C C12 0.6772(3) 0.9130(2) 1.30266(19) 0.0300(7) Uani d 1 . .
    H H12A 0.6561 0.9643 1.3197 0.045 Uiso calc 1 . .
    H H12B 0.7565 0.9124 1.3138 0.045 Uiso calc 1 . .
    H H12C 0.6578 0.8705 1.3342 0.045 Uiso calc 1 . .
    C C13 0.1149(2) 0.63767(17) 0.02161(19) 0.0216(6) Uani d 1 . .
    H H13 0.0728 0.6803 0.0310 0.026 Uiso calc 1 . .
    C C14 0.2914(3) 0.5656(2) 0.0675(2) 0.0379(8) Uani d 1 . .
    H H14A 0.2527 0.5324 0.0193 0.057 Uiso calc 1 . .
    H H14B 0.3153 0.5328 0.1180 0.057 Uiso calc 1 . .
    H H14C 0.3554 0.5899 0.0589 0.057 Uiso calc 1 . .
    C C15 0.2608(3) 0.6836(2) 0.1482(2) 0.0341(8) Uani d 1 . .
    H H15A 0.2041 0.7218 0.1485 0.051 Uiso calc 1 . .
    H H15B 0.3241 0.7119 0.1428 0.051 Uiso calc 1 . .
    H H15C 0.2836 0.6534 0.2005 0.051 Uiso calc 1 . .
    C C16 -0.0465(2) 0.43014(17) 0.80778(19) 0.0225(6) Uani d 1 . .
    H H16 -0.0392 0.4640 0.8539 0.027 Uiso calc 1 . .
    C C17 0.1313(2) 0.37298(19) 0.89417(19) 0.0273(7) Uani d 1 . .
    H H17A 0.1206 0.4090 0.9359 0.041 Uiso calc 1 . .
    H H17B 0.1975 0.3884 0.8824 0.041 Uiso calc 1 . .
    H H17C 0.1394 0.3186 0.9156 0.041 Uiso calc 1 . .
    C C18 0.0309(2) 0.32090(18) 0.7482(2) 0.0278(7) Uani d 1 . .
    H H18A -0.0347 0.3310 0.6997 0.042 Uiso calc 1 . .
    H H18B 0.0286 0.2666 0.7679 0.042 Uiso calc 1 . .
    H H18C 0.0963 0.3277 0.7324 0.042 Uiso calc 1 . .
_geom_special_details
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
    _geom_bond_atom_site_label_1
    _geom_bond_atom_site_label_2
    _geom_bond_site_symmetry_2
    _geom_bond_distance
    _geom_bond_publ_flag
    Cu1 N1 . 1.944(2) ?
    Cu1 N6 . 1.948(2) ?
    Cu1 O2 . 1.9760(17) ?
    Cu1 O1 . 1.9761(17) ?
    Cu1 O2 3_777 2.2773(17) ?
    Cu2 N3 . 1.962(2) ?
    Cu2 N2 . 1.964(2) ?
    Cu2 O7 . 1.9895(19) ?
    Cu2 O1 . 2.0061(17) ?
    Cu2 O5 3_777 2.2444(18) ?
    Cu3 N4 . 1.939(2) ?
    Cu3 N5 . 1.954(2) ?
    Cu3 O1 . 1.9879(18) ?
    Cu3 O6 . 1.9945(18) ?
    Cu3 O4 3_777 2.2759(18) ?
    S1 O3 . 1.4579(18) ?
    S1 O4 . 1.4691(18) ?
    S1 O5 . 1.4708(18) ?
    S1 O2 . 1.5055(18) ?
    Cl1 C2 . 1.729(3) ?
    Cl2 C5 . 1.723(3) ?
    Cl3 C8 . 1.726(3) ?
    O1 H1O . 0.775(17) ?
    O2 Cu1 3_777 2.2774(17) ?
    O4 Cu3 3_777 2.2759(18) ?
    O5 Cu2 3_777 2.2444(18) ?
    O6 C10 . 1.244(3) ?
    O7 H7A . 0.801(17) ?
    O7 H7B . 0.831(17) ?
    O8 C13 . 1.238(3) ?
    O9 C16 . 1.245(3) ?
    O10 H10A . 0.808(18) ?
    O10 H10B . 0.814(18) ?
    N1 C3 . 1.345(3) ?
    N1 N2 . 1.364(3) ?
    N2 C1 . 1.342(3) ?
    N3 C6 . 1.345(3) ?
    N3 N4 . 1.364(3) ?
    N4 C4 . 1.340(3) ?
    N5 C9 . 1.341(3) ?
    N5 N6 . 1.368(3) ?
    N6 C7 . 1.339(3) ?
    N7 C10 . 1.313(3) ?
    N7 C12 . 1.457(4) ?
    N7 C11 . 1.458(3) ?
    N8 C13 . 1.319(3) ?
    N8 C15 . 1.447(4) ?
    N8 C14 . 1.455(4) ?
    N9 C16 . 1.320(3) ?
    N9 C18 . 1.455(4) ?
    N9 C17 . 1.461(3) ?
    C1 C2 . 1.378(4) ?
    C1 H1 . 0.9300 ?
    C2 C3 . 1.380(4) ?
    C3 H3 . 0.9300 ?
    C4 C5 . 1.377(4) ?
    C4 H4A . 0.9300 ?
    C5 C6 . 1.382(4) ?
    C6 H6 . 0.9300 ?
    C7 C8 . 1.377(4) ?
    C7 H7 . 0.9300 ?
    C8 C9 . 1.377(4) ?
    C9 H9 . 0.9300 ?
    C10 H10 . 0.9300 ?
    C11 H11A . 0.9600 ?
    C11 H11B . 0.9600 ?
    C11 H11C . 0.9600 ?
    C12 H12A . 0.9600 ?
    C12 H12B . 0.9600 ?
    C12 H12C . 0.9600 ?
    C13 H13 . 0.9300 ?
    C14 H14A . 0.9600 ?
    C14 H14B . 0.9600 ?
    C14 H14C . 0.9600 ?
    C15 H15A . 0.9600 ?
    C15 H15B . 0.9600 ?
    C15 H15C . 0.9600 ?
    C16 H16 . 0.9300 ?
    C17 H17A . 0.9600 ?
    C17 H17B . 0.9600 ?
    C17 H17C . 0.9600 ?
    C18 H18A . 0.9600 ?
    C18 H18B . 0.9600 ?
    C18 H18C . 0.9600 ?
loop_
    _geom_angle_atom_site_label_1
    _geom_angle_atom_site_label_2
    _geom_angle_atom_site_label_3
    _geom_angle_site_symmetry_1
    _geom_angle_site_symmetry_3
    _geom_angle
    _geom_angle_publ_flag
    N1 Cu1 N6 . . 168.69(9) ?
    N1 Cu1 O2 . . 92.66(8) ?
    N6 Cu1 O2 . . 91.53(8) ?
    N1 Cu1 O1 . . 88.49(8) ?
    N6 Cu1 O1 . . 88.78(8) ?
    O2 Cu1 O1 . . 172.22(7) ?
    N1 Cu1 O2 . 3_777 96.06(8) ?
    N6 Cu1 O2 . 3_777 94.92(8) ?
    O2 Cu1 O2 . 3_777 82.09(7) ?
    O1 Cu1 O2 . 3_777 90.14(7) ?
    N3 Cu2 N2 . . 167.22(9) ?
    N3 Cu2 O7 . . 93.89(8) ?
    N2 Cu2 O7 . . 89.43(8) ?
    N3 Cu2 O1 . . 86.18(8) ?
    N2 Cu2 O1 . . 88.44(8) ?
    O7 Cu2 O1 . . 170.11(8) ?
    N3 Cu2 O5 . 3_777 96.85(8) ?
    N2 Cu2 O5 . 3_777 94.96(8) ?
    O7 Cu2 O5 . 3_777 97.26(7) ?
    O1 Cu2 O5 . 3_777 92.54(7) ?
    N4 Cu3 N5 . . 165.39(9) ?
    N4 Cu3 O1 . . 87.49(8) ?
    N5 Cu3 O1 . . 88.83(8) ?
    N4 Cu3 O6 . . 90.70(8) ?
    N5 Cu3 O6 . . 91.08(8) ?
    O1 Cu3 O6 . . 172.37(7) ?
    N4 Cu3 O4 . 3_777 96.70(8) ?
    N5 Cu3 O4 . 3_777 97.76(8) ?
    O1 Cu3 O4 . 3_777 96.49(7) ?
    O6 Cu3 O4 . 3_777 91.08(7) ?
    O3 S1 O4 . . 111.90(11) ?
    O3 S1 O5 . . 110.78(11) ?
    O4 S1 O5 . . 110.20(10) ?
    O3 S1 O2 . . 108.64(10) ?
    O4 S1 O2 . . 107.86(10) ?
    O5 S1 O2 . . 107.30(10) ?
    Cu1 O1 Cu3 . . 111.97(8) ?
    Cu1 O1 Cu2 . . 112.98(8) ?
    Cu3 O1 Cu2 . . 112.15(8) ?
    Cu1 O1 H1O . . 107(2) ?
    Cu3 O1 H1O . . 107(2) ?
    Cu2 O1 H1O . . 105(2) ?
    S1 O2 Cu1 . . 134.93(11) ?
    S1 O2 Cu1 . 3_777 127.14(10) ?
    Cu1 O2 Cu1 . 3_777 97.91(7) ?
    S1 O4 Cu3 . 3_777 118.91(11) ?
    S1 O5 Cu2 . 3_777 125.29(10) ?
    C10 O6 Cu3 . . 120.80(17) ?
    Cu2 O7 H7A . . 121(2) ?
    Cu2 O7 H7B . . 125(2) ?
    H7A O7 H7B . . 108(3) ?
    H10A O10 H10B . . 118(4) ?
    C3 N1 N2 . . 108.4(2) ?
    C3 N1 Cu1 . . 131.89(19) ?
    N2 N1 Cu1 . . 119.18(16) ?
    C1 N2 N1 . . 108.2(2) ?
    C1 N2 Cu2 . . 131.42(18) ?
    N1 N2 Cu2 . . 120.19(15) ?
    C6 N3 N4 . . 108.4(2) ?
    C6 N3 Cu2 . . 132.94(19) ?
    N4 N3 Cu2 . . 118.57(16) ?
    C4 N4 N3 . . 108.2(2) ?
    C4 N4 Cu3 . . 130.49(18) ?
    N3 N4 Cu3 . . 121.01(15) ?
    C9 N5 N6 . . 107.8(2) ?
    C9 N5 Cu3 . . 133.20(18) ?
    N6 N5 Cu3 . . 118.53(16) ?
    C7 N6 N5 . . 108.2(2) ?
    C7 N6 Cu1 . . 131.22(18) ?
    N5 N6 Cu1 . . 120.33(16) ?
    C10 N7 C12 . . 121.5(2) ?
    C10 N7 C11 . . 120.0(2) ?
    C12 N7 C11 . . 118.4(2) ?
    C13 N8 C15 . . 121.4(2) ?
    C13 N8 C14 . . 121.6(3) ?
    C15 N8 C14 . . 116.9(2) ?
    C16 N9 C18 . . 121.7(2) ?
    C16 N9 C17 . . 121.1(3) ?
    C18 N9 C17 . . 117.2(2) ?
    N2 C1 C2 . . 108.7(2) ?
    N2 C1 H1 . . 125.7 ?
    C2 C1 H1 . . 125.7 ?
    C1 C2 C3 . . 106.3(2) ?
    C1 C2 Cl1 . . 127.0(2) ?
    C3 C2 Cl1 . . 126.7(2) ?
    N1 C3 C2 . . 108.4(2) ?
    N1 C3 H3 . . 125.8 ?
    C2 C3 H3 . . 125.8 ?
    N4 C4 C5 . . 108.9(2) ?
    N4 C4 H4A . . 125.5 ?
    C5 C4 H4A . . 125.5 ?
    C4 C5 C6 . . 106.1(2) ?
    C4 C5 Cl2 . . 127.3(2) ?
    C6 C5 Cl2 . . 126.6(2) ?
    N3 C6 C5 . . 108.4(2) ?
    N3 C6 H6 . . 125.8 ?
    C5 C6 H6 . . 125.8 ?
    N6 C7 C8 . . 109.0(2) ?
    N6 C7 H7 . . 125.5 ?
    C8 C7 H7 . . 125.5 ?
    C7 C8 C9 . . 105.8(2) ?
    C7 C8 Cl3 . . 126.3(2) ?
    C9 C8 Cl3 . . 127.9(2) ?
    N5 C9 C8 . . 109.2(2) ?
    N5 C9 H9 . . 125.4 ?
    C8 C9 H9 . . 125.4 ?
    O6 C10 N7 . . 123.2(3) ?
    O6 C10 H10 . . 118.4 ?
    N7 C10 H10 . . 118.4 ?
    N7 C11 H11A . . 109.5 ?
    N7 C11 H11B . . 109.5 ?
    H11A C11 H11B . . 109.5 ?
    N7 C11 H11C . . 109.5 ?
    H11A C11 H11C . . 109.5 ?
    H11B C11 H11C . . 109.5 ?
    N7 C12 H12A . . 109.5 ?
    N7 C12 H12B . . 109.5 ?
    H12A C12 H12B . . 109.5 ?
    N7 C12 H12C . . 109.5 ?
    H12A C12 H12C . . 109.5 ?
    H12B C12 H12C . . 109.5 ?
    O8 C13 N8 . . 126.4(3) ?
    O8 C13 H13 . . 116.8 ?
    N8 C13 H13 . . 116.8 ?
    N8 C14 H14A . . 109.5 ?
    N8 C14 H14B . . 109.5 ?
    H14A C14 H14B . . 109.5 ?
    N8 C14 H14C . . 109.5 ?
    H14A C14 H14C . . 109.5 ?
    H14B C14 H14C . . 109.5 ?
    N8 C15 H15A . . 109.5 ?
    N8 C15 H15B . . 109.5 ?
    H15A C15 H15B . . 109.5 ?
    N8 C15 H15C . . 109.5 ?
    H15A C15 H15C . . 109.5 ?
    H15B C15 H15C . . 109.5 ?
    O9 C16 N9 . . 125.8(3) ?
    O9 C16 H16 . . 117.1 ?
    N9 C16 H16 . . 117.1 ?
    N9 C17 H17A . . 109.5 ?
    N9 C17 H17B . . 109.5 ?
    H17A C17 H17B . . 109.5 ?
    N9 C17 H17C . . 109.5 ?
    H17A C17 H17C . . 109.5 ?
    H17B C17 H17C . . 109.5 ?
    N9 C18 H18A . . 109.5 ?
    N9 C18 H18B . . 109.5 ?
    H18A C18 H18B . . 109.5 ?
    N9 C18 H18C . . 109.5 ?
    H18A C18 H18C . . 109.5 ?
    H18B C18 H18C . . 109.5 ?
loop_
    _geom_hbond_atom_site_label_D
    _geom_hbond_atom_site_label_H
    _geom_hbond_atom_site_label_A
    _geom_hbond_site_symmetry_A
    _geom_hbond_distance_DH
    _geom_hbond_distance_HA
    _geom_hbond_distance_DA
    _geom_hbond_angle_DHA
    _geom_hbond_publ_flag
    C18 H18B O3 1_445 0.96 2.64 3.494(4) 148.0 n
    C17 H17C O5 1_445 0.96 2.56 3.360(3) 140.7 n
    C15 H15C N2 4_575 0.96 2.63 3.406(4) 137.8 n
    C13 H13 O5 3_676 0.93 2.23 3.155(3) 170.2 y
    C10 H10 O4 3_777 0.93 2.30 2.971(3) 128.3 n
    C7 H7 O5 . 0.93 2.65 3.483(3) 149.4 n
    C7 H7 S1 . 0.93 2.95 3.610(3) 129.2 n
    C6 H6 O10 3_666 0.93 2.38 3.234(4) 153.3 y
    C4 H4A Cl3 3_677 0.93 2.93 3.484(3) 119.4 n
    C3 H3 O4 . 0.93 2.64 3.411(3) 140.4 n
    C3 H3 S1 . 0.93 2.99 3.616(3) 125.8 n
    O10 H10B O9 3_566 0.814(18) 1.96(2) 2.751(3) 165(4) y
    O10 H10A O3 4_575 0.808(18) 1.91(2) 2.700(3) 165(4) y
    O7 H7B O8 1_656 0.831(17) 1.829(18) 2.658(3) 175(3) y
    O7 H7A O10 3_666 0.801(17) 1.830(18) 2.625(3) 172(3) y
    O1 H1O O9 2_556 0.775(17) 1.953(18) 2.711(3) 166(3) y
    O1 H1O O9 2_556 0.775(17) 1.953(18) 2.711(3) 166(3) y
    O7 H7A O10 3_666 0.801(17) 1.830(18) 2.625(3) 172(3) y
    O7 H7B O8 1_656 0.831(17) 1.829(18) 2.658(3) 175(3) y
    O10 H10A O3 4_575 0.808(18) 1.91(2) 2.700(3) 165(4) y
    O10 H10B O9 3_566 0.814(18) 1.96(2) 2.751(3) 165(4) y
    C3 H3 S1 . 0.93 2.99 3.616(3) 125.8 n
    C3 H3 O4 . 0.93 2.64 3.411(3) 140.4 n
    C4 H4A Cl3 3_677 0.93 2.93 3.484(3) 119.4 n
    C6 H6 O10 3_666 0.93 2.38 3.234(4) 153.3 n
    C7 H7 S1 . 0.93 2.95 3.610(3) 129.2 n
    C7 H7 O5 . 0.93 2.65 3.483(3) 149.4 n
    C10 H10 O4 3_777 0.93 2.30 2.971(3) 128.3 .
    C13 H13 O5 3_676 0.93 2.23 3.155(3) 170.2 .
    C15 H15C N2 4_575 0.96 2.63 3.406(4) 137.8 n
    C17 H17C O5 1_445 0.96 2.56 3.360(3) 140.7 n
    C18 H18B O3 1_445 0.96 2.64 3.494(4) 148.0 n
_shelxl_version_number     2014/6
